Production processes

ABSTRACT

The present invention involves processes that utilize an olefinic compound, in particular, hexafluoropropene (HFP) or chlorotrifluoroethene (CFC-1113) as extracting agents in the purification of pentafluoroethane (HFC-125). These processes can utilize recovered HFP as a precursor for the production of heptafluoropropane (HFC-227) or other derivatives.

FIELD OF INVENTION

The present invention relates to processes for separatingpentafluoroethane (CHF₂-CF₃, HFC-125) from a mixture comprising HFC-125and chloropentafluoroethane (CF₃-CClF₂, CFC-115). The present inventionfurther relates to the production of heptafluoropropane (CF₃CHFCF₃ orCF₃CF₂CHF₂, HFC-227ea or HFC-227ca, collectively HFC-227).

BACKGROUND OF THE INVENTION

In the recent years, there has been an increasing concern about globalwarming. As a result, several chlorofluorocarbons (CFC's) that are knownto have an adverse environmental impact have been removed from themarketplace. In their place, new compounds have been introduced asflooding agents, streaming agents, blowing agents, propellants, andrefrigerants. However, some of these new compounds do not meetenvironmental safety requirements. Consequently, there is a constantneed to develop fluorocarbon compounds, especially hydrofluorocarbons,which have no chlorine. Two hydrofluorocarbons that are known to havedesirable properties are pentafluoroethane (HFC-125) andheptafluoropropane (HFC-227).

HFC-125 is a valuable hydrofluorocarbon (HFC) that is especially usefulas a refrigerant, blowing agent, propellant, or fire-extinguishingagent. HFC-125 can be prepared by a multi-step process starting withfluorination of tetrachloroethene (C₂Cl₄). The end products of themulti-step process include a mixture containing HFC-125,chloropentafluoroethane (CFC-115), and small amounts of otherfluorinated compounds.

HFC-227 is another valuable hydrofluorocarbon. One known startingmaterial for the production of HFC-227 is hexafluoropropene (CF₃CF═CF₂,HFP). HFP can be hydrofluorinated with hydrogen fluoride (HF) in thepresence of a suitable catalyst to form HFC-227 and other byproducts.Typically, in the final step of HFC-227 purification, these byproductsare separated out by simple distillation.

CFC-115 is an undesirable compound because it contains chlorine, and, asa result, its use is highly regulated. Thus, in the production ofHFC-125 for commercial use, it is necessary to separate HFC-125 fromCFC-115. Unfortunately, the mixture of HFC-125 and CFC-115 forms anear-azeotrope. At high concentrations of HFC-125, the relativevolatility of HFC-125 to CFC-115 is close to 1.0, making recovery ofpure HFC-125 from a mixture of HFC-125 and CFC-115 by simpledistillation difficult.

An azeotrope is a liquid mixture that exhibits a maximum or minimumboiling point relative to the boiling points of its components. Anazeotrope is homogeneous if only one liquid phase is present. Anazeotrope is heterogeneous if more than one liquid phase is present.Regardless, a characteristic of azeotropes is that the bulk liquidcomposition is identical to the vapor composition in equilibriumtherewith, and distillation of the azeotropic mixture is ineffective asa separation technique. For the purposes of this discussion, anear-azeotrope means a composition which behaves like an azeotrope(i.e., has constant-boiling characteristics or a tendency not tofractionate upon boiling or evaporation). Thus, the composition of thevapor formed during boiling or evaporation of such compositions is thesame as or substantially the same as the original liquid composition.Hence, during boiling or evaporation, the liquid composition, if itchanges at all, changes only to a minimal or negligible extent. This isto be contrasted with non-azeotrope compositions in which during boilingor evaporation, the liquid composition changes to a substantial degree.

Accordingly, the essential features of an azeotrope or a near-azeotropeare that at a given pressure, the boiling point of the liquidcomposition is fixed and that the composition of the vapor above theboiling composition is essentially that of the boiling liquidcomposition (i.e., no fractionation of the components of the liquidcomposition takes place). It is recognized in the art that both theboiling point and the weight percentages of each component of theazeotropic composition may change when the azeotrope or near-azeotropeliquid composition is subjected to boiling at different pressures. Thus,an azeotrope or a near-azeotrope may be defined in terms of the uniquerelationship that exists among components or in terms of thecompositional ranges of the components or in terms of exact weightpercentages of each component of the composition characterized by afixed boiling point at a specified pressure. It is also recognized inthe art that various azeotropic compositions including their boilingpoints at particular pressures may be calculated (see, e.g., W. Schotte,Ind. Eng. Chem. Process Des. Dev. 1980, 19, pp 432-439). Experimentalidentification of azeotropic compositions involving the same componentsmay be used to confirm the accuracy of such calculations and/or tomodify the calculations for azeotropic compositions at the same or othertemperatures and pressures.

It is known that pure HFC-125 as a near-azeotropic mixture with CFC-115can be recovered by a process of extractive distillation. In thisprocess, a suitable extracting agent that changes the relativevolatility of a component or the azeotrope is used. Examples ofextracting agents used in the purification of HFC-125 are disclosed inU.S. Pat. Nos. 5,087,329 and 5,928,479.

Extractive distillation processes for the purification of HFC-125usually include a step of separating the extracting agent from eitherHFC-125 or CFC-115 subsequent to the completion of the extractivedistillation. This additional separation process may add to the cost ofHFC-125 production even though the extracting agent may be reused.

SUMMARY OF INVENTION

The present invention provides processes for the production ofhalogenated hydrocarbons either alone or in combination with thesynthesis of olefinic derivatives. In one embodiment of the presentinvention, at least one halogenated hydrocarbon is purified from anear-azeotropic mixture comprising at least one halogenated hydrocarbonand at least one halocarbon by extractive distillation using an olefinicextracting agent. In this particular embodiment, the olefinic extractingagent is converted into a derivative compound.

In another embodiment of the present invention, HFC-125 is purified froma mixture containing CFC-115 by extractive distillation, usinghexafluoropropene (HFP) or chlorotrifluoroethene (CClF=CF₂, CFC-1113) asan extracting agent. One feature of this particular embodiment is thatthe extracting agent can be recovered and reused in the purification ofHFC-125 as set forth herein. In an alternative embodiment, the recoveredextracting agent can be used as a starting material for the productionof fluorocarbons like HFC-227.

In a specific embodiment of the present invention, the process ofrecovering HFC-125 comprises the steps of: (a) providing a first mixturecomprising HFC-125 and CFC-115, (b) distilling the first mixture in thepresence of hexafluoropropene (HFP) to separate HFC-125 from a secondmixture comprising HFP and CFC-115. The distilling process may beextractive distillation, in which HFP is an extracting agent.

According to another embodiment of the invention, the process mayfurther include the steps of: (c) recovering HFC-125 as an overheadproduct and (d) recovering the second mixture as a bottom product.

According to a further embodiment, the process may further include thestep of: (e) purifying HFP from the second mixture to produce a thirdmixture comprising CFC-115 and the step of (f) recovering HFP.Optionally, the process may include the step of re-using the recoveredHFP as an extracting agent, as described herein.

Another embodiment of the present invention is directed to a processcomprising the steps of: (a)-(d), as described, and the steps of: (g)adding HF to the second mixture to form a fourth mixture, (h) convertingHFP in the fourth mixture by hydrofluorination in the presence of asuitable catalyst to HFC-227 to produce a fifth mixture, (i) separatingthe fifth mixture into HFC-227 and a sixth mixture comprising CFC-115,and (j) recovering HFC-227.

A further embodiment of the present invention is directed to a processcomprising the steps of: (a)-(f), as described, and the steps of: (k)adding HF to the recovered HFP, (l) converting the recovered HFP byhydrofluorination to HFC-227 in the presence of a suitable catalyst toproduce a seventh mixture, (m) separating the seventh mixture intoHFC-227 and byproducts, and (n) recovering HFC-227.

In another embodiment, the process comprises the steps of: (a)-(f), asdescribed, and the step of converting HFP to at least one HFP derivativeor a fluoropolymer.

In an alternative embodiment of the present invention, the processcomprises the steps of: (o) providing a first mixture comprising HFC-125and CFC-115, (p) distilling the first mixture in the presence ofCFC-1113 to separate HFC-125 from an eighth mixture comprising CFC-1113and CFC-115, (q) recovering HFC-125 as an overhead product, and (r)recovering the eighth mixture as a bottom product. The distillingprocess may be extractive distillation, in which HFP is an extractingagent.

In still another embodiment, the process comprises the steps of (o)-(r)and the steps of: (s) adding HF to the eighth mixture to produce a ninthmixture, (t) converting CFC-1113 in the ninth mixture in the presence ofa suitable catalyst to a fluoroethane to make a tenth mixture, andrecycling the tenth mixture to a hydrofluorocarbon production process.In one embodiment, the fluoroethane is1-chloro-1,2,2,2-tetrafluoroethane (CHClFCF₃, HCFC-124).

The above and other embodiments, aspects, alternatives and advantages ofthe present invention will become more apparent from the followingdetailed description of the present invention taken in conjunction withthe examples.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of promoting an understanding of the principles of theinvention, reference will now be made to the embodiments illustrated inthe drawings and specific language will be used to describe the same. Itwill nevertheless be understood that no limitation of the scope of theinvention is thereby intended. The invention includes any alterationsand further modifications in the illustrated devices and describedmethods and further applications as would be conveyed to one skilled inthe art to which the invention relates.

The present invention overcomes the shortcomings of the prior art byproviding innovative processes for producing hydrofluorocarbons byseparating mixtures of near-azeotrope halogenated hydrocarbons withextracting agents and subsequently converting the extracting agent to aderivative compound that can be separated from at least one of thehalogenated hydrocarbons from the near-azeotropic mixture.

In one embodiment, the present invention involves the use of anextracting agent, namely HFP, that can be used to purify HFC-125 from amixture-comprising HFC-125 and CFC-115. The mixture may contain mostlyHFC-125 and only minute amounts of CFC-115 and other fluorocarbonbyproducts. HFP is an important monomer used to produce organic fluorinematerials and is readily available in the marketplace.

The use of HFP as an extracting agent for the separation of alkanes hasnever been described in the prior art. It is commonly known that similarcompounds are attracted to each other. Thus, typically, in order toseparate chlorine containing alkanes from non-chlorine containingalkanes, another chlorine containing alkane is used as an extractingagent. As an alkene, HFP is structurally different from the alkanesdisclosed as extracting agents in the U.S. Pat. No. 5,087,329. Thisstructural difference in combination with the fact that HFP contains nochlorine made its usefulness as an extracting agent for separatingHFC-125 from CFC-115 unexpected. The use of HFP and fluorinated alkenesas extracting agents is demonstrated below in non-limiting Example 1.

EXAMPLE 1 Screening of extracting Agents for Vapor Phase Separation ofHFC-125 and CFC-115

A 50 cc stainless steel sample cylinder fitted with a pressure gauge andvalve with a septum port was chilled to −78° C. and a known amount ofHFC-125 and CFC-115 was charged to the cylinder. This mixture was shakenand allowed to warm to ambient temperature and the vapor phase wassampled for subsequent analysis by gas chromatography (GC).

The cylinder was then re-cooled to −78° C. and a desired amount of thechosen extraction solvent was added to the vessel. The mixture was thenallowed to warm to ambient temperature, at which time, it was shaken andallowed to equilibrate for 3 to 12 hours before it was re-sampled for GCanalysis.

All GC data of this and the following examples were taken by sampling acollection or storage vessel or the appropriate sample port with a 50 to250 μL airtight syringe fitted with an on/off valve. This collectedsample was injected on either an HP-5890 or 5890II GC equipped with aVarian plot fused silica column (30 m×0.32 mm ID). All analyses weredone using a time-temperature program which had an initial temperatureand time of 70° C. and 15 min followed by a ramp to 140° C. at a rate of15° C./min and a final time of 20 min. Selection of column type, samplesize and analysis conditions are well known to those skilled in the artof GC. All amounts noted were based on area percent. To verify theidentity of each compound, analyses were performed using massspectrometry.

TABLE I is a result of the GC analyses of vapor phase content of HFC-125and CFC-115 in the starting mixture and the mixture with extractingagent that absorbs CFC-115. As shown in TABLE I, relative volatility ofCFC-115 changed with the addition of different solvents. The volatilityof CFC-115 was relatively low with the addition of the CFC-solvents,like 1,1,2-trichloro-1,2,2-trifluoroethane (CCl₂FCClF₂, CFC-113) and1,2-dichloro-1,1,2,2-tetrafluoroethane (CClF₂CF₂Cl, CFC-114). Thus,these solvents, CFC-113 and CFC-114, performed well in the separation ofCFC-115 from HFC-125, as shown by the increase in the percent of HFC-125or the decrease in the percent of CFC-115 in the vapor phase. Asexpected, the similar compounds like dichlorohexafluoropropane (C₃F₆Cl₂,CFC-216) and chloroheptafluoropropane (C₃F₇Cl, CFC-217) also exhibitedgood extracting ability for CFC-115. However, being chlorofluorocarbons,these compounds are not desirable extracting agents because they arehighly regulated suspect ozone depleting compounds.

The efficiency of the fluoro-olefins, namely CFC-1113, HFP, HFC-1243zf(CF₃CH═CH₂, TFP), and HFC-1225zc (CF₃CH═CF₂, PFP) varied. CFC-1113 andHFP demonstrated a surprising ability to extract CFC-115 from HFC-125.However, since HFP contains no chlorine, it may be more useful as anextracting agent.

In contrast to HFP and CFC-1113, the olefins HFC-1243zf and HFC-1225zchad little or no extractive power. In addition, chloroform (CHCl₃) didnot appear to be an effective extracting agent for the separation ofCFC-115. TABLE I GC Analysis of the vapor phase content of HFC-125 andCFC-115 in starting mixture and mixture with extracting agent thatabsorbs CFC-115 % HFC-125 % CFC-115 Extracting Extracting RelativeExtracting At agent At agent Volatility of agent start added Changestart added CFC-115 CHCl₃ 98.28 98.28 0.00 1.72 1.72 1.00 HFC- 99.0299.04 0.02 0.98 0.96 0.98 1243zf HFC- 99.14 99.17 0.03 0.86 0.83 0.961225zc C₂Cl₄ 98.28 98.49 0.21 1.72 1.51 0.88 CFC-217 98.28 98.52 0.241.72 1.48 0.86 CFC-216 98.28 98.54 0.26 1.72 1.46 0.85 CCl₄ 98.28 98.540.26 1.72 1.46 0.85 HFP 99.02 99.18 0.16 0.98 0.82 0.84 CFC-1113 99.1499.31 0.17 0.86 0.69 0.80 CFC-114 98.28 98.78 0.50 1.72 1.22 0.71CFC-113 98.28 98.82 0.54 1.72 1.18 0.69

In certain embodiments, the present invention involves utilizingolefinic extracting agents in two different ways. First, the olefinicextracting agent can be used to purify HFC-125 from a mixture comprisingHFC-125 and CFC-115. Relatively pure HFC-125 is recovered as theoverhead product, while the majority of the olefinic extracting agent isrecovered as a mixture with CFC-115 as a bottom product. In oneembodiment, the olefinic extracting agent is HFP. In another embodiment,the olefinic extracting agent is CFC-1113.

Second, after it is used as an extracting agent, the olefinic extractingagent can be recovered and used as a precursor for the production ofextracting agent derivatives or fluoropolymers. As an olefin, therecovered extracting agent lends itself to hydrohalogenation by additionacross the double bond.

In one embodiment, HF is added across the double bond of HFP to produceHFC-227. In another embodiment, HF may be added across the double bondof CFC-1113 to produce HCFC-124. In these embodiments, the relativevolatility of the extracting agent derivative is sufficiently disparatefrom CFC-115 that the derivative can be readily separated by knownchemical separation techniques such as distillation. Further, CFC-1113may also be converted to HFC-125 or a mixture of HFC-125 and HCFC-124,in which case it may be recycled to the HFC-125 CFC-115 purificationprocess to produce more HFC-125.

These types of hydrohalogenation reactions are commonly performed in thepresence of a catalyst. Suitable gas phase catalysts include activatedcarbon, chromium oxide, nickel, copper, iron, or aluminum oxide.Suitable liquid phase catalysts include antimony chloride, molybdenum,and tantalum. It is contemplated that other compounds and syntheticschemes can be used to derivatize the extracting agent. The resultingcompound may be recovered or recycled back to the separation process.

According to a specific embodiment of the present invention, a processfor separating HFC-125 from CFC-115 is provided. The process includes astep of (a) providing a first mixture comprising HFC-125 and CFC-115.The first mixture may be derived from a hydrofluorination reaction oftetrachloroethene, or other similar processes. The first mixture mayalso contain small amounts of other hydrofluorination byproducts such as1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114),2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), or hexafluoroethane(FC-116). The percent concentration of HFC-125 and CFC-115 in the firstmixture may vary. The first mixture may contain more than 90% ofHFC-125.

The first mixture is fed to a fractionation column. In this specificembodiment of the invention, the process further comprises the step of(b) distilling the first mixture in the presence of HFP to separateHFC-125 from a second mixture comprising HFP and CFC-115. During thisstep, HFP is added to the upper section of the fractionation column. Asmuch as about 50% HFP by weight of HFC-125 may be used, although morethan 50% HFP by weight of HFC-125 may be used if desired. However,preferably 20% HFP by weight of HFC-125 is used.

The distillation is performed at a condition that allows HFC-125 to passsubstantially free of CFC-115 to the top of the column where it iscondensed. Some of the HFC-125 may be returned as reflux.Simultaneously, HFP and CFC-115 pass to the bottom of the column as asecond mixture. It is possible for the second mixture to also containresidual HFC-125 and other compounds that are present in the firstmixture. Finally, in a particular embodiment, the process includes thesteps of (c) recovering BFC-125 as an overhead product and (d)recovering the second mixture as a bottom product. One embodiment ofthis process is demonstrated below in non-limiting Example 2.

EXAMPLE 2 Vapor Phase Separation of HFC-125 from CFC-115 Using HFP as anExtracting Agent

This procedure demonstrates the effective removal of CFC-115 fromstreams of the first mixture comprising HFC-125 and CFC-115, by the useof HFP as an extracting agent.

The apparatus used was a 92 in. packed, schedule 40, carbon steeldistillation column fitted with a reboiler, overhead condenser, overheadreflux loop, timed take-off valves, and multiple feed points. Thisevacuated column was charged with 584 g of the first mixture comprising97.928% of HFC-125 and 2.073% of CFC-115, by weight. This mixture wasallowed to equilibrate at a reflux ranging from 14 to 29 cc/min. HFP wasthen fed into the column at an average rate of 1.98 g/min, while takingoff CFC-115 and HFP at a rate of 1.75 g/min as the bottom product fromthe reboiler.

The operation was continued over 2348 minutes. The total amount of HFPadded was 4438 g. During this time, the relative ratio of HFC-125 toCFC-115 in the overhead of the column increased from 87 to 8194 (TABLEII). This ratio represents approximately 121 ppm (0.0121% GC-Area) ofCFC-115 remaining in the overhead fraction (TABLE II).

The recovery from the reboiler shows that most of the HFP was recapturedin the reboiler or the bottom fraction. This bottom fraction alsocontained CFC-115 and residual HFC-125 (TABLE II).

At the end of the operation, the initial charge, including the amount ofthe first mixture and the total amount of HFP used, is compared to thefinal recovery in both the reboiler and the overhead fractions. Theresults show a total mass balance accountability of 96.6%. TABLE IIExtractive distillation using HFP as an extracting agent to separateHFC-125 from CFC-115 Column Overhead Column Reboiler Time HFP HFC-125CFC-115 Relative ratio of HFC-125 CFC-115 HFP (min) Feed (g) (% GC-Area)(% GC-Area) HFC-125 to CFC-115 (% GC-Area) (% GC-Area) (% GC-Area) 5 998.8076 1.1361 87 96.5055 2.4569 0.3507 71 134 98.3079 0.8889 111 267505 99.4534 0.4757 209 1.9543 0.2929 97.7323 515 973 99.0789 0.3670 270764 1444 99.4312 0.4172 238 0.0264 0.0241 99.9367 954 1803 98.78820.1890 523 1158 2189 99.7811 0.1492 669 0.0359 0.0055 99.9473 1357 256599.0762 0.0797 1243 1573 2973 99.8564 0.0653 1529 0.0301 0.0013 99.95311918 3625 99.2493 0.0286 3465 2102 3973 99.8944 0.0303 3297 0.02650.0035 99.9554 2234 4222 99.4617 0.0268 3711 2348 4438 99.3941 0.01218194 0.0356 0.0023 99.9620

In another embodiment of the present invention, the process furtherincludes the step of (e) purifying HFP in the second mixture to producerelatively pure HFP and a third mixture comprising CFC-115 and the stepof (f) recovering HFP. The third mixture may include residual HFP andHFC-125. In addition, the third mixture may also include small amountsof byproducts, as indicated above. The recovered HFP from thispurification step may contain a minute amount of CFC-115 and otherbyproducts. The purification step may involve any appropriate techniqueincluding distillation. The purification of HFP by simple distillationis demonstrated below in non-limiting Example 3.

EXAMPLE 3 Purification of HFP

To demonstrate this process, 507 grams of a mixture containing 90.17% ofHFP, 9.798% of HFC-125, and 0.025% of CFC-115 (see TABLE III) wascharged to an apparatus consisting of a 92 in. packed, schedule 40,carbon steel distillation column fitted with a reboiler, overheadcondenser, and overhead reflux loop. This mixture was allowed toequilibrate with a steady reflux for 224 minutes. The distillation wasrun at a pressure of about 122-123 psig. The boiler temperature was setat about 31.4° C., and the overhead temperature was set at about 27° C.The overhead and reboiler compositions were checked by GC analysis. Thecolumn was then equilibrated for another 100 minutes to obtain furtherhomogeneity of the HFP in the reboiler of the column (see TABLE III).This demonstrates that the longer the distillation was run, the higherpurity of HFP was obtained. This level of purity is acceptable forrecycle to the HFC-125 extractive distillation system or to be used as araw material in subsequent downstream reactions. TABLE III Separation ofHFP from HFC-125 and CFC-115 by distillation Equilibrium % GC-Area Time(min) HFC-125 CFC-115 HFP Starting Mixture 0 9.798 0.025 90.174 Overhead244 18.379 0.035 81.586 Reboiler 244 2.769 0.014 97.209 Overhead 34418.491 0.034 81.460 Reboiler 344 1.049 0.013 98.934

The recovered HFP may be recycled to be used as an extracting agent inthe process of recovering HFC-125 described herein. In anotherembodiment, the recovered HFP may be converted to at least one of HFPderivatives such as HFC-227, or polymers such as elastomers, plastomers,resins, and fluoropolymers.

Another specific embodiment of the present invention comprises the stepsof (a)-(d), as described herein, and the further steps of (g) adding HFto the second mixture to form a fourth mixture and (h) converting HFP inthe fourth mixture to HFC-227 by hydrofluorination to form a fifthmixture. The benefits of this embodiment are demonstrated by way ofnon-limiting Example 4 below.

EXAMPLE 4 Converting HFP to HFC-227 by Selective Hydrofluorination inthe Presence of HFC-125 and CFC-115

A 34 cc alloy-600 reactor tube was charged with 13.1 g of activatedcarbon catalyst and dried overnight at 155° C. with a nitrogen purge.The reaction outlet was configured with an aqueous scrubber filled withdilute caustic followed by a Drierite tube, GC sampling port, andoptional cold trap. Three different mixtures were used as the startingmaterial in the reaction runs (#1-3). Each mixture comprises HFP and ntsof CFC-115 and HFC-125 (see TABLE IV). In the reaction run #4,relatively pure HFP was used as the starting material for TABLE IVComposition (% GC) of starting material for four reaction runs offluorination of HFP to HFC-227 % GC-Area Run # HFP HFC-125 CFC-115 199.960 0.024 0.009 2 99.396 0.540 0.055 3 86.979 12.750 0.419 4 99.991 ——

Specific conditions of each fluorination reaction run using thematerials shown in TABLE IV are shown in TABLE V. For each run, thestarting material was supplied to the reactor tube described above. HFwas first added to the reactor tube at a rate of about 70 to 74 cc/min.The flow rate of the starting material was about 47 to 60 cc/min. Theratio of HF to HFP ranged from 1.28 to 1.60. The fluorination reactionwas temperature of about 200° C. (see TABLE V). The contact time rangedfrom 9.16 to 10.08 seconds. TABLE V Fluorination conditions of fourfluorination reaction runs using four starting materials shown in TABLEIV Flow rate Contact Starting Material Molar Temp. Time HF HFP/115/125Ratio Run # (° C.) (sec) (cc/min) (cc/min) HF:HFP 1 203 9.16 72.80 55.711.28 2 205 9.58 70.00 59.90 1.29 3 204 9.66 74.23 47.46 1.57 4 204 10.0873.05 43.81* 1.60*HFP only

The result of each fluorination reaction run shown in TABLE V isreported in TABLE VI. Percent conversion of HFP to HFC-227 ranged fromabout 92.13 to 97.24, while selectivity ranged from about 85 to about 99%. The amounts of HFC-125 and CFC-115 did not substantially change fromwhat was present in the starting materials (see TABLE IV and VI). Thus,the data in TABLE VI indicate that olefins can be selectivelyfluorinated without causing any serious side reactions or lowering ofconversion while allowing HFC-125 and CFC-115 to pass through the systemessentially unchanged. TABLE VI The results of the fluorination processbased on the conditions shown in TABLE V HFC-227 Conversion SelectivityHFC-125 CFC-115 Run # % % % GC-Area % GC-Area 1 92.13 99.27 0.02310.0065 2 95.54 98.58 0.5617 0.0421 3 96.62 85.08 13.1312 0.4361 4 97.2499.06 — —

In accordance with another embodiment of the present invention, aprocess includes the steps of (a)-(d), (g)-(h), and the step (i)separating the fifth mixture into HFC-227 and a sixth mixture comprisingCFC-115. The sixth mixture may further comprise HFC-125 and otherfluorination byproducts. The separation can be performed bydistillation. Finally, this specific embodiment further includes thestep of (j) recovering relatively pure HFC-227. This embodiment isdemonstrated below by way of non-limiting Example 5.

EXAMPLE 5 Separation of HFC-227 from HFC-125 and CFC-115

A mixture containing mainly HFC-227 (57.24%), HFC-125 (29.44% ), andCFC-115 (13.32%) was used as the starting material to demonstrate theprocess of HFC-227 separation. An evacuated apparatus consisting of a 92in. packed, schedule 40, carbon steel distillation column fitted with areboiler, overhead condenser, and overhead reflux loop was charged with719 grams of the above described mixture. This mixture was allowed toequilibrate at a reflux ranging from 1.86 to 2.46 cc/min over a 1417minute time period. The overhead product and the bottom product werecollected at three different distillation conditions (see TABLE VII).The content of both the overhead and the bottom products was determinedby GC. The results shown in TABLE VII indicate that the majority ofHFC-227 was separated in the bottom fraction while HFC-125 and CFC-115were removed as distillates. When the reboiler temperature was increasedfrom 28.2° C. to 55.3° C. and the vapor pressure was raised from 132psig to 143 psig, the reflux increased from 1.85 cc/min to 2.46 cc/min,and a significant increase in purity of the HFC-227 in the bottomfraction was observed. Essentially pure HFC-227 (99.92%) could berecovered under one of the conditions tested (144 psig, reboilertemperature 54.8° C., overhead temperature 21.9° C., reflux 2.46cc/min), while only a small amount of HFC-227 was removed in theoverhead fraction. The levels of HFC-227 purity recovered wereacceptable for commercial use. The resulting CFC-115 and HFC-125 caneither be destroyed, recycled or reacted to form other desirable anduseful materials. TABLE VII Separation of HFC-227 at three differentdistillation conditions % GC-Area Condition HFC-227 MFC-125 CFC-115Starting Mixture 57.24 29.44 13.32 A^(a) Overhead 32.68 47.93 19.39Reboiler 97.98 0.57 1.45 B^(b) Overhead 5.79 73.59 20.59 Reboiler 99.780.098 0.12 C^(c) Overhead 3.77 74.31 21.91 Reboiler 99.92 0.065 0.012^(a)132 psig, reboiler temperature 28.2° C., overhead temperature 21.5°C., reflux 1.85 cc/min^(b)143 psig, reboiler temperature 55.3° C., overhead temperature 21.6°C., reflux 2.46 cc/min^(c)144 psig, reboiler temperature 54.8° C., overhead temperature 21.9°C., reflux 2.46 cc/min

A further embodiment of the present invention involves a process whichcomprises the steps of (a)-(f) and the steps of: (k) adding HF to thepurified HFP, (l) converting the purified HFP by hydrofluorination toHFC-227 in the presence of a suitable catalyst to form a seventhmixture, (m) separating the seventh mixture into HFC-227 andfluorination byproducts, and (n) recovering relatively pure HFC-227. Anexample of converting relatively pure BFP to HFC-227 is demonstrated inTABLES IV-VI (see run #4).

According to one embodiment, the suitable catalyst is active carbon, butother catalysts that have been previously described are contemplated.

Additional objects, advantages, and other novel features of theinvention will become apparent to those skilled in the art uponexamination of the foregoing or may be learned with practice of theinvention. The foregoing description of the embodiments of the inventionhas been presented for purposes of illustration and description. It isnot intended to be exhaustive or to limit the invention to the preciseform disclosed. Obvious modifications or variations are possible in thelight of the above teachings. Embodiments were chosen and described toprovide the best illustrations of the principals of the invention andtheir practical application, thereby enabling one of ordinary skill inthe art to utilize the invention in various embodiments and with variousmodifications as are suited to the particular use contemplated. All suchmodifications and variations are within the scope of the invention asdetermined by the appended claims when interpreted in accordance withthe breadth to which they are fairly, legally, and equitably entitled.

1-30. (canceled)
 31. A production process comprising: providing a first mixture comprising a first compound and a second compound, the first mixture having a first ratio of the first compound to the second compound; exposing the mixture to a C-3 olefin to form a second mixture, the second mixture comprising the C-3 olefin and the first mixture; and removing a third mixture from the second mixture, the third mixture having a second ratio of the first compound to the second compound, the second ratio being different than the first ratio.
 32. The production process of claim 31 wherein the C-3 olefin is hexafluoropropene.
 33. The production process of claim 31 wherein both the first and second compounds are C-2 compounds.
 34. The production process of claim 33 wherein both the first and second compounds comprise at least one halogen.
 35. The production process of claim 34 wherein one or both of the first and second compounds comprise one or both of F and Cl.
 36. The production process of claim 35 wherein the first compound comprises Cl and the second compound comprises F.
 37. The production process of claim 36 wherein the first compound is C₂F₅Cl and the second compound is C₂F₅H.
 38. The production process of claim 37 wherein the C-3 olefin comprises a halogen.
 39. The production process of claim 38 wherein the C-3 olefin comprises F.
 40. The production process of claim 39 wherein the C-3 olefin is C₃F₆.
 41. The production process of claim 31 wherein: the first compound comprises Cl; the second compound comprises F; and the C-3 olefin comprises F.
 42. The production process of claim 41 wherein both the first and second compounds are C-2 compounds.
 43. The production process of claim 31 wherein the C-3 olefin comprises F.
 44. The production process of claim 43 wherein the C-3 olefin is C₃F₆.
 45. The production process of claim 31 wherein: the first compound comprises Cl; the second compound comprises F; and the first ratio is greater than the second ratio.
 46. A production process comprising exposing a reaction mixture to an extracting agent to separate a product compound of the reaction mixture from at least one reactant compound of the reaction mixture, wherein the extracting agent comprises a C-3 olefin.
 47. The production process of claim 46 wherein the product compound is a halogen exchange reaction product of the one reactant compound.
 48. The production process of claim 47 wherein: the product compound comprises F; and the one reactant compound comprises Cl.
 49. The production process of claim 48 wherein: the product compound is C₂F₅H; and the one reactant compound is C₂F₅Cl.
 50. The production process of claim 49 wherein the C-3 olefin comprises F.
 51. The production process of claim 46 wherein the C-3 olefin is C₃F₆. 